FIELD OF INVENTION

[0001] The present invention relates to novel molecular compounds. In more detail, it relates to molecular compounds consisting of self-associating compounds with 4 or more diffusive hydrogen bond sites and polymers having hydrogen bond sites, and to methods for aligning and modifying polymers having hydrogen bond sites, with the self-associating compounds with or more diffusive hydrogen bond sites.

BACKGROUND ART

[0002] Molecular compounds are molecular assemblies that two or more compounds are bound through relatively weak interactions, other than covalent bonds, represented by hydrogen bonds or van der Waals forces. Molecular compounds containing polymers as constituent compounds are expected to have polymer effects in addition to molecular alignment controls due to intermolecular interactions. Because of this, the molecular compounds have attracted attentions in recent years as a technique for constructing composite materials called composites, polymer alloys or hybrids. Higher functions given when forming composite are closely related to molecular alignment controls of polymers in polymer assemblies. For example, biomolecules are often involved in expressing functions by becoming composite with or assembling with other molecules, rather than functioning alone. Another example is that, as seen in nucleic acids, a assembly itself plays important roles in expressing higher functions in many cases. As described above, phenomena of polymer assemblies not only are mere interests as materials but also are expected as fields with potentials beyond our present common knowledge, such as retaining and transferring information and formation of specific sites.

[0003] Polymer assemblies are formed based on weak, secondary, non-covalent bonding forces working between chains or in a chain, such as Coulomb forces, hydrogen bonding forces, hydrophobic bonding forces, charge transfer bonding forces and van der Waals forces. In particular, assemblies based on hydrogen bonds, which are direction-specific interactions, are expected to be a promising technique to promote highly functional materials by means of forming composites, thanks to the relationship between molecular alignment controls and functions, which has attracted attention in recent years.

[0004] A concrete example of polymer assemblies is a complex between polymers. For example, a polymer assembly of polymethacrylic acid and poly(N-vinylpyrolidone) via cooperative hydrogen bonds is known to have very interesting physico-chemical and dynamic properties that are completely different from those of constituent polymers [Makromol. Chem., Rapid Commun., Vol. 1, Page 591 (1980)]. A assembly of polymethacrylic acid and polyethylene glycol, formed via a similar interaction, has been reported to be a mechanochemical system having a deforming function responding to the environment, which is not found in the constituent polymers [Makromol. Chem., Vol. 176, Page 2761 (1975)].

[0005] Such assemblies based on complexes between polymers exist in various forms ranging from very regular shapes such as polymer crystals, polymer liquid crystals or regular higher-order structures composed of assembled sub-units found in certain types of biomolecules, to irregular ones found in phase separation phenomena, such as precipitate, gel, coacervate and emulsion.

[0006] An effect of a molecular compound containing polymers as constituent compounds comes from the large molecular weights and multi-functionality of polymers: Interactions, separations and cooperative actions, based on functional groups arranged freely in space, are exemplified as polymer effects. However, it is difficult to fix interaction points and to control interaction forces among polymers of which many functional groups exist densely on a single, flexible chain. Therefore it is not satisfactory with respect to stably producing molecular compounds with fixed compositions and structures.

[0007] A complex between a low molecule and a polymer, utilizing interactions with the low molecule is known as a method for controlling the chain structure of the constituent polymer. This method using low molecules, which are easily designed and handled, can easily create a large variety of structures relating to expressing functions, and has attracted attention as a method for aligning and modifying a polymer, in such a way that the constituent polymer is crystallized, made to have a higher melting point or made insoluble due to pseudo crosslinking. Almost no compositions are known to be widely used in general and be good for practical use in terms of industrial and basic materials. Only a few examples have been disclosed, including, as those based on van der Waals forces, complexes containing polyethylene oxide and urea as constituent compounds [J. Polym. Sci., B, Vol. 2, Page 363 (1964)], those containing polyethylene and urea as constituent compounds [J. Macromol. Sci. Phys., Vol. 8, Page 277 (1973)], those containing syndiotactic polystyrene and benzene, and an aromatic hydrocarbon such as toluene or iodine or carbon tetrachloride, as constituent compounds [Polymer, Vol. 34, No. 23, Page 4841 (1993)], and crystalline molecular compounds containing polyethylene oxide and p-dihalogenobenzenes as constituent compounds [Polymer Communications, Vol. 32, No. 15, Page 477 (1991)]; and, as those based on hydrogen bonds, those containing polyethylene imine and water as constituent compounds [Macromolecule, Vol. 14, Page 315 (1981)], those containing polyethylene oxide and hydroquinone, resorucinol or p-nitrophenol as constituent compounds [Macromol. Symp., Vol. 114, Page 51 (1997)] and crystalline molecular compounds containing poly(N-vinylpyrolidone) and 3,5-dihydroxybenzoic acid [Supramolecular Science, Vol. 2, Page 41 (1995)].

[0008] Functions of the polymer assemblies based on the complexes between low molecules and polymers are determined depending on how the low molecules coordinate to the polymers. It becomes therefore very important to control association forms between low molecules and polymers when polymer assemblies are designed and manufactured. It is however difficult to produce polymer assemblies with fixed compositions and structures selectively and stably, because known complexes between low molecules and polymers, based on van der Waals forces are weakly direction-specific in molecular associations. In known complexes between low molecules and polymers, based on hydrogen bonds, constituent polymers applicable with low molecules are very restricted. Besides, functional groups in low molecules, which rule hydrogen bonds, are not arranged properly in terms of directions in the actions. Functions supposed from hydrogen-bonding associations between low molecules and polymers have not been expressed satisfactorily.

[0009] In recent years, polymer assemblies based on complexes between low molecules and polymers have attracted attention particularly with respect to functionalities in formulations, waste water treatments, energy transducers, conductors, bio-model reactions and the like. There is only a very little information on roles played by low molecules as well as on solid structures. Compositions that are very satisfactory from the viewpoint of industrially valuable materials have not been found yet.

DISCLOSURE OF THE INVENTION

[0010] It is an object of the present invention to provide molecular compounds useful in the fields of state-of-the-art materials, such as formulations, waste water treatments, energy transducers, conductors and bio-model reactions, in a way that interaction points and forces working inside polymer assemblies are fixed and further controlled so that constituent polymers are aligned and modified. It is also an object of the present invention to provide methods for aligning and/or modifying polymers having hydrogen bond sites.

[0011] To solve the above problems, the inventors have studied in earnest, and found that it was easy and efficient to control the molecular alignment of hydrogen bonding polymers and modify the polymers, which are very important for building composite materials, if diffusive hydrogen bonds are present between molecules in polymer assemblies. Factors controlling the diffusive hydrogen bonds between molecules were studies in detail. As a result, it was found that self-associating compounds having 4 or more diffusive hydrogen bond sites formed, with a wide range of hydrogen bonding polymers, stable molecular compounds that were excellent in moldability and had regular domains, and that the obtained molecular compounds had excellent properties useful in the fields of state-of-the-art materials such as formulations, waste water treatments, energy transducers, conductors and bio-model reactions. Thus the present invention has been completed.

[0012] The present invention relates to a molecular compound consisting of a self-associating compound with 4 or more diffusive hydrogen bond sites and a polymer having hydrogen bond sites (claim 1); a molecular compound according to claim 1 in which the self-associating compound with 4 or more diffusive hydrogen bond sites is a tetrakis aryl compound represented by Formula (1) [wherein, X is (CH ₂ ) _n or p-phenylene; n is 0, 1, 2 or 3; Y is hydroxyl, carboxyl or optionally substituted amino; and R ¹ and R ² are each hydrogen, lower alkyl, optionally substituted phenyl, halogen or lower alkoxy] (claim 2); and a molecular compound according to claim 1 or 2 in which the polymer having hydrogen bond sites is one or more polymers selected from the group consisting of polyethers, polyalcohols, polyamines, polyphenols, polyacrylic acids, polyvinyl ethers, polyvinyl ketones, polyvinyl heterocyclic compounds, polycarboxylic acid vinyls, polysaccharides and polyamino acids (claim 3). 2

[0013] The present invention also relates to a method for aligning and/or modifying a polymer having hydrogen bond sites with a self-associating compound with 4 or more diffusive hydrogen bond sites (claim 4); a method for the alignment and/or modification according to claim 4 in which the self-associating compound with 4 or more diffusive hydrogen bond sites is a tetrakis aryl compound represented by Formula (1) (claim 5); and a method for the alignment and/or modification according to claim 4 or 5 in which the polymer having hydrogen bond sites is one or more polymers selected from the group consisting of polyethers, polyalcohols, polyamines, polyphenols, polyacrylic acids, polyvinyl ethers, polyvinyl ketones, polyvinyl carboxylic asids, polyvinyl heterocyclic compounds, polycarboxylic acid vinyls, polysaccharides and polyamino acids (claim 6). 3

[0014] The molecular compounds of the present invention are a compound that two or more constituent compounds able to exist stably on their own and containing one or more polymers are bound via hydrogen bonds. Examples of the compound include hydrates, solvates, adducts, clathrate compounds, molecular composites, polymer blends and polymer alloys.

[0015] Furthermore, the molecular compounds of the present invention are usually crystalline solids, and may be amorphous or oily, or sometimes polymorphic. They exist in various forms, such as liquid crystal, gel, coacervate and emulsion. Regardless of these forms, any molecular compounds containing self-associating compounds with 4 or more diffusive hydrogen bond sites and polymers having hydrogen bond sites as constituent compounds are all covered by the present invention.

[0016] In a tetrakis aryl compound represented by Formula (1) of the present invention, X is (CH ₂ ) _n or p-phenylene; n is 0, 1, 2 or 3; Y is hydroxyl, carboxyl or optionally substituted amino; and R ¹ and R ² are each hydrogen, lower alkyl, optionally substituted phenyl, halogen or lower alkoxy. There are no restrictions on tetrakis aryl compounds of the present invention if the compounds have 4 or more hydrogen bonding functional groups in the molecules, are of diffusive type that the functional groups can self-associate between molecules, and can form molecular compounds with polymers having hydrogen bond sites. One or more appropriate compounds can be selected for use.

[0017] Examples of tetrakis aryl compounds used in the present invention include 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-methyl-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-chloro-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3,5-dichloro-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-bromo-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3,5-dibromo-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-t-butyl-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3,5-di-t-butyl-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-fluoro-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3,5-difluoro-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-methoxy-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3,5-dimethoxy-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-phenyl-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3,5-diphenyl-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-fluoro-5-methyl-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-chloro-5-methyl-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-bromo-5-methyl-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-methoxy-5-methyl-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-t-butyl-5-methyl-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-phenyl-5-methyl-4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-chloro-5-bromo-4-hydroxyphenyl)ethane and 1,1,2,2-tetrakis(3-chloro-5-phenyl-4-hydroxyphenyl)ethane.

[0018] Examples of tetrakis aryl compounds used in the present invention also include 1,1,3,3-tetrakis(4-hydroxyphenyl)propane, 1,1,3,3-tetrakis(3-methyl-4-hydroxyphenyl)propane, 1,1,3,3-tetrakis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1,3,3-tetrakis(3-chloro-4-hydroxyphenyl)propane, 1,1,3,3-tetrakis(3,5-dichloro-4-hydroxyphenyl)propane, 1,1,3,3-tetrakis(3-bromo-4-hydroxyphenyl)propane, 1,1,3,3-tetrakis(3,5-dibromo-4-hydroxyphenyl)propane, 1,1,3,3-tetrakis(3-phenyl-4-hydroxyphenyl)propane, 1,1,3,3-tetrakis(3,5-diphenyl-4-hydroxyphenyl)propane, 1,1,3,3-tetrakis(3-methoxy-4-hydroxyphenyl)propane, 1,1,3,3-tetrakis(3,5-dimethoxy-4-hydroxyphenyl)propane, 1,1,3,3-tetrakis(3-t-butyl-4-hydroxyphenyl)propane, and 1,1,3,3-tetrakis(3,5-di-t-butyl-4-hydroxyphenyl)propane.

[0019] Examples of tetrakis aryl compounds used in the present invention also include 1,1,4,4-tetrakis(4-hydroxyphenyl)butane, 1,1,4,4-tetrakis(3-methyl-4-hydroxyphenyl)butane, 1,1,4,4-tetrakis(3,5-dimethyl-4-hydroxyphenyl)butane, 1,1,4,4-tetrakis(3-chloro-4-hydroxyphenyl)butane, 1,1,4,4-tetrakis(3,5-dichloro-4-hydroxyphenyl)butane, 1,1,4,4-tetrakis(3-methoxy-4-hydroxyphenyl)butane, 1,1,4,4-tetrakis(3,5-dimethoxy-4-hydroxyphenyl)butane, 1,1,4,4-tetrakis(3-bromo-4-hydroxyphenyl)butane, 1,1,4,4-tetrakis(3,5-dibromo-4-hydroxyphenyl)butane, 1,1,4,4-tetrakis(3-t-butyl-4-hydroxyphenyl)butane, and 1,1,4,4-tetrakis(3,5-t-butyl-4-hydroxyphenyl)butane.

[0020] Examples of tetrakis aryl compounds used in the present invention also include 1,1,5,5-tetrakis(4-hydroxyphenyl)pentane, 1,1,5,5-tetrakis(3-methyl-4-hydroxyphenyl)pentane, 1,1,5,5-tetrakis(3,5-dimethyl-4-hydroxyphenyl)pentane, 1,1,5,5-tetrakis(3-chloro-4-hydroxyphenyl)pentane, 1,1,5,5-tetrakis(3,5-dichloro-4-hydroxyphenyl)pentane, 1,1,5,5-tetrakis(3-methoxy-4-hydroxyphenyl)pentane, 1,1,5,5-tetrakis(3,5-dimethoxy-4-hydroxyphenyl)pentane, 1,1,5,5-tetrakis(3-bromo-4-hydroxyphenyl)pentane, 1,1,5,5-tetrakis(3,5-dibromo-4-hydroxyphenyl)pentane, 1,1,5,5-tetrakis(3-t-butyl-4-hydroxyphenyl)pentane, and 1,1,5,5-tetrakis(3,5-di-t-butyl-4-hydroxyphenyl)pentane.

[0021] Examples of tetrakis aryl compounds used in the present invention also include α,α,α′,α′-tetrakis(4-hydroxyphenyl)-p-xylene, α,α,α′,α′-tetrakis(3-methyl-4-hydroxyphenyl)-p-xylen e, α,α,α′,α′-tetrakis(3,5-dimethyl-4-hydroxyphenyl)-p-e thane, α,α,α′,α′-tetrakis(3-chloro-4-hydroxyphenyl)-p-xylen e, α,α,α′,α′-tetrakis(3,5-dichloro-4-hydroxyphenyl)-p-x ylene, α,α,α′,α′-tetrakis(3-bromo-4-hydroxyphenyl)-p-xylene , α,α,α′,α′-tetrakis(3,5-dibromo-4-hydroxyphenyl)-p-xy lene, α,α,α′,α′-tetrakis(3-t-butyl-4-hydroxyphenyl)-p-xyle ne, α,α,α′,α′(3,5-di-t-butyl-4-hydroxyphenyl)-p-xylene, α,α,α′,α′-tetrakis(3-fluoro-4-hydroxyphenyl)-p-xylen e, α,α,α′,α′-tetrakis(3,5-difluoro-4-hydroxyphenyl)-p-x ylene, α,α,α′,α′-tetrakis(3-methoxy-4-hydroxyphenyl)-p-xyle ne, α,α,α′,α′-tetrakis(3,5-dimethoxy-4-hydroxyphenyl)-p- xylene, α,α,α′,α′-tetrakis(3-phenyl-4-hydroxyphenyl)-p-xylen e, α,α,α′,α′-tetrakis(3,5-diphenyl-4-hydroxyphenyl)-p-x ylene, α,α,α′,α′-tetrakis(3-fluoro-5-methyl-4-hydroxyphenyl )-p-xylene, α,α,α′,α′-tetrakis(3-chloro-5-methyl-4-hydroxyphenyl )-p-xylene, α,α,α′,α′-tetrakis(3-bromo-5-methyl-4-hydroxyphenyl) -p-xylene, α,α,α′,α′-tetrakis(3-methoxy-5-methyl-4-hydroxypheny l)-p-xylene, α,α,α′,α′-tetrakis(3-t-butyl-5-methyl-4-hydroxypheny l)-p-xylene, α,α,α′,α′-tetrakis(3-chloro-5-bromo-4-hydroxyphenyl) -p-xylene and α,α,α′,α′-tetrakis(3-chloro-5-phenyl-4-hydroxyphenyl )-p-xylene.

[0022] Examples of tetrakis aryl compounds used in the present invention also include 1,1,2,2-tetrakis(4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3-methyl-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3,5-dimethyl-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3-chloro-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3,5-dichloro-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3-bromo-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3,5-dibromo-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3-t-butyl-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3,5-di-t-butyl-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3-fluoro-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3,5-difluoro-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3-methoxy-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3,5-dimethoxy-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3-phenyl-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3,5-diphenyl-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3-fluoro-5-methyl-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3-chloro-5-methyl-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3-bromo-5-methyl-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3-methoxy-5-methyl-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3-t-butyl-5-methyl-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3-phenyl-5-methyl-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3-chloro-5-bromo-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(3-chloro-5-phenyl-4-carboxyphenyl)ethane, 1,1,2,2-tetrakis(4-aminophenyl)ethane, 1,1,2,2-tetrakis(3-methyl-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3,5-dimethyl-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3-chloro-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3,5-dichloro-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3-bromo-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3,5-dibromo-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3-t-butyl-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3,5-di-t-butyl-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3-fluoro-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3,5-difluoro-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3-methoxy-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3,5-dimethoxy-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3-phenyl-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3,5-diphenyl-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3-fluoro-5-methyl-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3-chloro-5-methyl-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3-bromo-5-methyl-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3-methoxy-5-methyl-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3-t-butyl-5-methyl-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3-phenyl-5-methyl-4-aminophenyl)ethane, 1,1,2,2-tetrakis(3-chloro-5-bromo-4-aminophenyl)ethane and 1,1,2,2-tetrakis(3-chloro-5-phenyl-4-aminophenyl)ethane.

[0023] Of the above tetrakis aryl compounds represented by Formula (1) and used in the present invention, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 1,1,2,2-tetrakis(3-methyl-4-hydroxyphenyl)ethane, 1,1,4,4-tetrakis(4-hydroxyphenyl)butane, 1,1,5,5-tetrakis(4-hydroxyphenyl)pentane, 1,1,2,2-tetrakis(4-carboxyphenyl)ethane and 1,1,2,2-tetrakis(4-aminophenyl)ethane are particularly preferred from the viewpoint of performances such as molecular alignment, chemical stabilization and modification of the polymers having hydrogen bond sites.

[0024] The tetrakis aryl compounds of the present invention are usually crystalline solids, and may be amorphous or oily, or sometimes polymorphic. Regardless of these forms, the tetrakis aryl derivatives of Formula (1) are all covered by the present invention.

[0025] As for a polymer having hydrogen bond sites and used in the present invention, one or more appropriate polymers can be selected for use from known polymers having hydrogen bond sites and that can be classified into any of polyethers, polyalcohols, polyamines, polyphenols, polyacrylic acids, polyvinyl ethers, polyvinyl ketones, polyvinyl heterocyclic compounds, polycarboxylic acid vinyls, polysaccharides and polyamino acids. There are no particular restrictions on the polymers having hydrogen bond sites if they form molecular compounds with tetrakis aryl compounds represented by the said Formula (1) and used in the present invention, whether they are single polymers or copolymers. Examples of such polymers are described in the following:

[0026] Polyethers include polyoxymethylene, polyacetal, polyethylene oxide, polyethylene glycol, polybutylene glycol, polytetramethylene oxide, polyoxymethylene alkyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkyphenyl ethers, polyethylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hardened castor oil, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, polyoxyethylene alkylphenylformamide condensates, polyethylene glycol dialkyl ethers, polyethylene glycol dilaurate, polyoxyethylene glycol dioleate, polyethylene glycol distearate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dibenzoate, polyethylene glycol diglycidyl ether, polyethylene glycol divinyl ether, polyethylene glycol-n-alkylsulfopropyl ethers, polyethylene glycol biphenyl ether methacrylate, polyethylene glycol bisaminopropylterminate, polyethylene glycol bis(carboxymethyl) ether, polyethylene glycol bisethylhexanoate, polypropylene oxide, polypropylene glycol, polypropylene glycol monoalkyl ethers, polypropylene glycol dialkyl ethers, polypropylene glycol fatty acid esters, polypropylene glycol acrylate, polypropylene glycol diacrylate, polyethylene glycol dibenzoate, polyethylene glycol diglycidyl ether, oxyethylene glycol-oxypropylene glycol copolymers, oxyethylene glycol-oxypropylene glycol copolymers, oxyethylene-oxypropylene glycol copolymers, oxyethylene-oxypropylene alkyl ether copolymers, polyether rubber, crown ethers and polymers substituted with crown ethers.

[0027] Polyalcohols include polyvinyl alcohol and vinyl alcohol-vinyl pyrolidone copolymers. Polyamines include polyethylene imine, poly(N-acetylethylene imine), poly(N-formylethylene imine), polyvinyl amine and poly(N,N-dimethyl-N′,N′,N″,N″-tetramethylene phosphoramide). Polyphenols include polyvinyl phenol, polyphenol imine diethanol isophthalate and phenol-formaldehyde resins. Polyacrylic acids include polyacrylic acid, polymethacrylic acid, polyitaconic acid, polymethyl methacrylate, polymethyl methacrylate, polyacrylamide, polydimethylaminoethyl methacrylate, polyhydroxyethyl acrylate, poly(N-hydroxymethylacrylamide), poly(N-hydroxyethylacrylamide), poly(N-iso-propylacrylamide), polyglycidyl methacrylate, polymethoxypolyethylene glycol monomethacrylate and poly(diethoxy-n-methylitaconate).

[0028] Polyvinyl ethers include polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl-iso-butyl ether, polyvinyl acetal, polyvinyl butylal, polyvinyl formal and polyethoxy-ethoxy-ethoxy-vinyl ether. Polyvinyl ketones include polyvinyl methyl ketone and polyvinyl phenyl ketone. Polyvinyl heterocyclic compounds include polyvinyl pyrolidone, polyvinyl pyridine, polyvinyl piperazine, polyvinyl imidazole, polyvinyl imidazoline, polyvinyl carbazole, polyvinyl adenine and polyvinyl cytosine. Polycarboxylic acid vinyls include polyvinyl acetate, polyvinyl cinnamate and maleic anhydrate-vinyl acetate copolymers. Polysaccharides include starch, amylose, cycloamylose, amiropectin, cellulose, alginic acid, glycogen, chitin and hyaluronic acid. Polyamino acids include polyglycine, polyserine, polylysine, oxytocin and polyglutamic acid.

[0029] A polymer used in the present invention is a compound consisting of molecules that a large number of one type or several types of constituent units are mutually combined via chemical bonds. In more detail, it refers to a compound that the number of the constituent units does not affect the properties of the molecules. There are no particular restrictions on the molecular weight of a polymer used in the present invention if the polymer forms a molecular compound with a tetrakis aryl compound of the said Formula (1). Polymers having molecular weights particularly in the range of 200 to 2,000,000 are preferably used from the viewpoint of forming direction-specific hydrogen bonds and performances such as organization, chemical stabilization and modification due to the formation.

[0030] A molecular compound of the present invention may be produced in a way that a tetrakis aryl compound of the said Formula (1) and a polymer having hydrogen bond sites and forming a molecular compound, such as those described above, are directly mixed or are mixed in water or organic solvents, or by a casting method in which the two compounds are mixed in water or organic solvents followed by gradual evaporation of the solvents. It is possible to produce a molecular compound consisting of multiple constituents of 3 or more by reacting 2 or more types of polymers with a tetrakis aryl compound. It is also possible to produce a target molecular compound by that a molecular compound consisting of a tetrakis aryl derivative and a specific polymer having hydrogen bond sites is first formed, and then the obtained molecular compound is reacted with another polymer having hydrogen bond sites according to a method mentioned above. Furthermore, a molecular compound containing ions, molecules or the like as third components can be produced in a way that ions, molecules or the like are additionally added as third components to a tetrakis aryl derivative and a polymer having hydrogen bond sites and are reacted according to such methods as those mentioned above.

[0031] A molecular compound of the present invention may vary in a ratio of constituent compounds composing it, depending on conditions. It can be confirmed that a substance obtained according to a method mentioned above is surely a molecular compound by such techniques as thermal analysis (TG/DTA), infrared absorption spectra (IR), X-ray diffraction patterns and ¹³ C-CP/MAS-solid-state NMR spectra. The composition of a molecular compound can be confirmed by thermal analysis, ¹ H-NMR spectra, gel permeation chromatography (GPC), high performance liquid chromatography (BPLC), elementary analysis and the like.

[0032] The molecular compounds of the present invention are preferably used in any form including crystal, liquid crystal, gel, precipitated solid, coacervate, emulsion and liquid. It is however preferable that the compounds are of solid forms, such as crystal, liquid crystal, gel or precipitated solid, from the viewpoint of functions such as basic materials for formulations, waste water treating materials, energy transducers, conductors and bio-model reaction sites and for the purposes of producing stable molecular compounds excellent in moldability and with regular domains and fixed compositions. When crystalline, the same molecular compound may be polymorphic. X-ray diffraction patterns are mainly examined to check whether a compound is crystalline. A solid structure containing a polymorphic compound can be confirmed by such a means as X-ray diffraction patterns, ¹³ C-CP/MAS-solid-state NMR spectra, polarization microscope and electron microscope. Intermolecular interactions in a molecular compound can be confirmed using infrared absorption spectra (IR) and ¹³ C-CP/MAS solid state NMR spectra.

[0033] The method of the present invention for aligning and/or modifying a polymer is characterized in that the conformation and assembly form of a polymer having hydrogen bond sites, that is, a hydrogen bonding polymer, which is one of the components of a molecular compound, is controlled, depending on the characteristics of a tetrakis aryl compound used. In the methods of the present invention for aligning and/or modifying polymers, whether a polymer composing a molecular compound can take a target structure depends on a form of the hydrogen bond between each tetrakis aryl molecule and the polymer. In other words, the molecular compound of the present invention is a multi-molecular assembly that a tetrakis aryl compound and a hydrogen bonding polymer are associated via hydrogen bonds. When a self-associating, low molecular compound having diffusive hydrogen bond sties is reacted to a hydrogen bonding polymer, direction-specific hydrogen bonds are formed between polymers and at regular intervals in polymer chains so as to make the polymer orientation and organization. Thus it becomes possible to align and modify the hydrogen bonding polymer.

[0034] For example, when a tetrakis aryl compound working only as a proton donor to a hydrogen bonding polymer is used, the polymer chains are aligned and organized and the polymer structure is optimized according to the regular domains formed due to the association among the tetrakis aryl molecules. On the other hand, if a tetrakis aryl compound working as both a proton donor and proton acceptor to a hydrogen bonding polymer is used, the tetrakis aryl molecule and polymer are regularly aligned and organized alternatively by three-dimensionally developed hydrogen bonds, to form a stable molecular compound.

[0035] For example, when 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane (TEP), which is a tetrakis aryl compound working as a proton donor to polyethylene oxide (PEO), is reacted with PEO at a ratio of ethylene oxide (EO) unit/TEP=5 to 15, the EO chains are oriented and organized with rapid exchange between the gauche and trans conformations, according to the three-dimensional lattice space formed by the hydrogen bonds between TEP molecules. As a result, a stable TEP-PEO molecular compound having a melting point of 160° C. or above is formed. On the other hand, when TEP working as both a proton donor and proton acceptor to polyethylene imine (PEI) is reacted with PEI at a ratio of ethylene imine (EI) unit/TEP=5 to 15, the EI chains are oriented and organized by the three-dimensional hydrogen bonds formed alternatively between PEI and TEP molecules so that an extremely stable TEP-PEI molecular compound with a decomposition point of 250° C. or above is formed. As described above, in the methods of the present invention for aligning and modifying polymers utilizing the formation of molecular compounds, it becomes possible to align and modify a hydrogen bonding polymer with functions that have been difficult to control, if a self-associating, low molecule with diffusive hydrogen bond sites is present when the polymer assembles.

[0036] There are no particular restrictions on how to use the molecular compounds of the present invention. For example, two or more types of molecular compounds, each consisting of different constituent compounds, can be mixed for use. The molecular compounds of the present invention can be used together with other substances, whether inorganic or organic, as long as they do not damage target functions, and can also be used by adding to resins, coatings, and their materials and material compositions. In addition, the molecular compounds of the present invention can be used as base materials or excipients for the chemical stabilization, non-volatilization, pulverization, granulation and making tablets, of functional substances, or as gelling agents to gel liquid substances. In addition, the molecular compounds of the present invention can also be used as clathrate compounds containing atoms or molecules. A clathrate compound here refers to a substance of which there are holes of appropriate size inside three-dimensional structures formed by atoms or molecules bound and other atoms or molecules are placed inside the holes by means of non-covalent interactions at a fixed composition ratio. The molecular compounds of the present invention used as three-dimensional structures having inner holes may be formed from 3 or more constituent compounds. Atoms or molecules to be included inside are not necessarily single ones but two or more. The molecular compounds of the present invention can also be used as media to transfer functional substances or as specific reaction sites.

[0037] For example, a tetrakis aryl compound of the said Formula (1) and a hydrogen bonding polymer are reacted according to one of direct mixing, solvent and casting methods in the presence of a pyrethroid type pesticide such as Allethrin; quaternary ammonium salt type bactericide such as benzalkonium chloride or cetyl pyridinium chloride; antimicrobial antimolding agent such as 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, zinc-2-pyridinethiol-1-oxide, 2,2′-dithiobis(pyridin-N-oxide), 2-bromo-2-nitropropan-1,3-diol or 2,3,3-triiodoallyl alcohol; terpene type perfume such as hinokitiol, cineole, citronellol or geraniol; or metal salt such as lithium perchlorate, sodium iodide, potassium iodide, sodium thiocyanate or potassium thiocyanate. Then, a gel or solid molecular compound can be produced, stably containing the said pesticide, bactericide, antimicrobial antimolding agent, perfume or metal salt, in the polymer assembly phase.

[0038] It can be confirmed that the substance obtained according to the method is surely a molecular compound by such a means as thermal analysis (TG/DTA), infrared absorption spectra (IR), X-ray diffraction patterns and ¹³ C-CP/MAS solid state NMR spectra. The composition of the molecular compound can be confirmed by thermal analysis, atomic absorption analysis, elementary analysis and the like.

[0039] Molecular compounds, such as those mentioned above, are given functions including slow release, reduction of skin irritation, chemical stabilization, non-volatilization, pulverization, ionization and selective separation of useful substances, in addition to the actions that the pesticide, bactericide, antimicrobial antimolding agent, perfume or metal salt has originally. Therefore, the molecular compounds are extremely useful as functional materials with new properties.